EP3460026B1 - Procédé pour la conversion de pétrole brut en produits pétrochimiques ayant une efficacité en carbone améliorée - Google Patents

Procédé pour la conversion de pétrole brut en produits pétrochimiques ayant une efficacité en carbone améliorée Download PDF

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Publication number
EP3460026B1
EP3460026B1 EP18205192.0A EP18205192A EP3460026B1 EP 3460026 B1 EP3460026 B1 EP 3460026B1 EP 18205192 A EP18205192 A EP 18205192A EP 3460026 B1 EP3460026 B1 EP 3460026B1
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Prior art keywords
distillate
produced
hydrocracking
crude oil
resid
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EP18205192.0A
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German (de)
English (en)
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EP3460026A1 (fr
Inventor
Andrew Mark Ward
Ravichander Narayanaswamy
Arno Johannes Maria OPRINS
Vijayanand RAJAGOPALAN
Egidius Jacoba Maria SCHAERLAECKENS
Raul VELASCO PELAEZ
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SABIC Global Technologies BV
Saudi Basic Industries Corp
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SABIC Global Technologies BV
Saudi Basic Industries Corp
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/34—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts
    • C10G9/36—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts with heated gases or vapours
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12—Inorganic carriers
    • C10G47/14—Inorganic carriers the catalyst containing platinum group metals or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12—Inorganic carriers
    • C10G47/16—Crystalline alumino-silicate carriers
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12—Inorganic carriers
    • C10G47/16—Crystalline alumino-silicate carriers
    • C10G47/20—Crystalline alumino-silicate carriers the catalyst containing other metals or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/10—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only cracking steps
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/14—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural parallel stages only
    • C10G65/18—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural parallel stages only including only cracking steps
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
    • C10G69/06—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of thermal cracking in the absence of hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00002—Chemical plants
    • B01J2219/00004—Scale aspects
    • B01J2219/00006—Large-scale industrial plants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • B01J2219/00027—Process aspects
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2219/00033—Continuous processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00002—Chemical plants
    • B01J2219/00042—Features relating to reactants and process fluids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00277—Apparatus
    • B01J2219/00351—Means for dispensing and evacuation of reagents
    • B01J2219/0038—Drawing
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/104—Light gasoline having a boiling range of about 20 - 100 °C
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1044—Heavy gasoline or naphtha having a boiling range of about 100 - 180 °C
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1048—Middle distillates
    • C10G2300/1051—Kerosene having a boiling range of about 180 - 230 °C
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1048—Middle distillates
    • C10G2300/1055—Diesel having a boiling range of about 230 - 330 °C
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1048—Middle distillates
    • C10G2300/1059—Gasoil having a boiling range of about 330 - 427 °C
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/20—C2-C4 olefins
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/30—Aromatics
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

Definitions

  • the present invention relates to an integrated process to convert crude oil into petrochemical products comprising crude oil distillation, hydrocracking and olefins synthesis.
  • a crude oil refinery can be integrated with downstream chemical plants such as a pyrolysis steam cracking unit in order to increase the production of high-value chemicals at the expense of the production of fuels.
  • US 3,702,292 describes an integrated crude oil refinery arrangement for producing fuel and chemical products, involving crude oil distillation means, hydrocracking means, delayed coking means, reforming means, ethylene and propylene producing means comprising a pyrolysis steam cracking unit and a pyrolysis products separation unit, catalytic cracking means, aromatic product recovery means, butadiene recovery means and alkylation means in an inter-related system to produce a conversion of crude oil to petrochemicals of about 50% and a conversion of crude oil to fuels of about 50%.
  • the present invention relates to an integrated process according to claim 1, to convert crude oil into petrochemical products. This process is also presented in figures 1-4 which are further described herein below.
  • the present invention provides a process to convert crude oil into petrochemical products comprising crude oil distillation, hydrocracking and olefins synthesis, which process comprises subjecting a hydrocracker feed to hydrocracking to produce LPG and BTX and subjecting LPG produced in the process to olefins synthesis, wherein said hydrocracker feed comprises:
  • petrochemical products such as C2 and C3 olefins
  • C2 and C3 olefins are produced by subjecting crude oil to crude oil distillation and to subject specific crude oil fractions thus obtained to a refinery process.
  • the carbon efficiency of an integrated process to convert crude oil into petrochemical products can be improved by hydrocracking one or more of naphtha, kerosene and gasoil, i.e. the C5+ hydrocarbons, to produce LPG and to subsequently convert the LPG produced by hydrocracking into olefins, when compared to a process wherein the same crude oil fractions are directly subjected to steam cracking.
  • carbon efficiency in terms of the conversion of crude oils into petrochemicals or “carbon efficiency” relates to the wt-% of carbon comprised in petrochemical products of the total carbon comprised in the crude, wherein said petrochemical products are selected from the group consisting of ethylene, propylene, butadiene, butylene-1, isobutylene, isoprene, cyclopentadiene (CPTD), benzene, toluene, xylene and ethylbenzene.
  • CPTD cyclopentadiene
  • the process of the present invention involves subjecting the C5+ hydrocarbons to hydrocracking to produce LPG and subjecting the thus obtained LPG to olefins synthesis.
  • the C+ hydrocarbons are preferably not subjected to olefins synthesis.
  • the term "one or more of naphtha, kerosene and gasoil produced by crude oil distillation in the process” means that said one or more of naphtha, kerosene and gasoil are produced by the crude distillation process step comprised in the integrated process of the present invention.
  • the term "refinery unit-derived light-distillate and/or refinery unit-derived middle-distillate produced in the process” means that said refinery unit-derived light-distillate and/or refinery unit-derived middle-distillate are produced by a refinery unit process step comprised in the integrated process of the present invention.
  • the hydrocracker feed comprises:
  • the hydrocracker feed used in the present invention comprises:
  • the hydrocracker feed used in the present invention comprises:
  • the hydrocracker feed used in the present invention comprises:
  • the hydrocracker feed used in the present invention comprises:
  • the hydrocracker feed used in the present invention comprises:
  • the prior art describes processes for producing petrochemical products from specific hydrocarbon feeds such as specific crude oil fractions and/or refinery unit-derived distillates.
  • WO 2006/137615 A1 describes a process for increasing the production of C2-C4 light olefin hydrocarbons by integrating a process for producing a light olefin hydrocarbon carbon compound from a hydrocarbon feedstock comprising feeding said hydrocarbon feedstock into a pyrolysis furnace to conduct a pyrolysis reaction, feeding the separated pyrolysis gasolines produced in the pyrolysis reaction, a hydrocarbon feedstock and hydrogen in a reaction area to convert the hydrocarbon feedstock in the presence of a catalyst into an aromatic hydrocarbon compound and a non-aromatic hydrocarbon that is rich in LPG through a hydrocracking reaction.
  • reaction products of the hydrocracking reaction is subjected to gas-liquid separation wherein the resulting gaseous comprising ethane and LPG is circulated to the same compression and fractionation process used to separate the products produced in the pyrolysis reaction.
  • WO 2006/137615 A1 further describes that the C2-C4 paraffins recovered in the compression and fractionation process used to separate the products produced in the pyrolysis reaction may be circulating into the pyrolysis furnace.
  • WO 2006/137615 A1 The process of WO 2006/137615 A1 is inter alia characterized in that the hydrocarbon feedstock has a boiling point of 30-250°C and may be selected from the group consisting of reformate, pyrolysis gasoline, fluidized catalytic cracking gasoline, C9+ aromatic-containing mixture, naphtha, and mixtures thereof.
  • WO 2006/137615 A1 accordingly does not disclose an integrated process for converting crude oil into petrochemical products.
  • WO 2006/137615 A1 teaches that hydrocarbon feedstock should be directly subjected to liquid steam cracking.
  • WO 2006/137615 A1 does not teach that it would be advantageous to first subject the hydrocarbon feedstock to hydrocracking to produce LPG and to subject the thus obtained LPG to olefins synthesis instead of subjecting said hydrocarbon feedstock directly to olefins synthesis.
  • US 2007/0062848 A1 describes process to treat hydrocarbon compounds comprising two or more fused aromatic rings to saturate at least one ring and then cleave the resulting saturated ring from the aromatic portion of the compound to produce a C2-4 alkane stream and an aromatic stream.
  • the C2-4 alkane stream produced in the process is fed to a hydrocarbon cracker so that the hydrogen from the cracker may be used to saturate and cleave the compounds comprising two or more fused aromatic rings.
  • WO 2006/137615 A1 does not disclose that crude oil fractions such as naphtha and diesel or distillates produced in the process, such as catalytic cracker gasoline or aromatic ring cleavage unit-derived gasoline, can be subjected to hydrocracking to produce LPG and BTX.
  • US 2003/0221990 A1 describes a multi-stage hydrocracking process in which light products from the first stage, such as naphtha, kerosene and diesel, are joined with naphtha, kerosene and diesel from other sources and recycled from fractionation to a second stage (or subsequent stage) hydrocracker in order to produce lighter products, such as gas and naphtha.
  • US 2003/0221990 A1 does not disclose olefins synthesis.
  • US 3,891,539 describes a hydrocracking process for converting heavy hydrocarbon oil into fuels.
  • the process of US 3,891,539 inter alia comprises hydrocracking heavy hydrocarbon oil charge in a first hydrocracking zone in the presence of a porous hydrocracking catalyst to mainly gas-oil and hydrocracking the thus obtained gas-oil in a second hydrocracking zone to produce gasoline.
  • US 3,891,539 does not disclose process steps suitable for the production of petrochemicals such as BTX or olefins.
  • US 3,449,460 describes a process for upgrading aromatic hydrocarbon feedstock having a boiling point of up to 200°C comprising separating said feedstock into a first fraction boiling between 80°C and 120°C and a second fraction boiling between 120°C and 200°C and subjecting the first fraction to a first and subsequent stages of a hydro-upgrading zone , subjecting said second fraction into a hydrogenation zone and supplying the hydrogenated fraction to a second stage of a hydro-upgrading zone.
  • US 3,449,460 does not disclose a process for converting hydrocarbons having a boiling point of 200°C or more.
  • US 3,449,460 does not disclose olefins synthesis.
  • crude oil refers to the petroleum extracted from geologic formations in its unrefined form.
  • crude oil will also be understood to include that which has been subjected to water-oil separations and/or gas-oil separation and/or desalting and/or stabilization.
  • Any crude oil is suitable as the source material for the process of this invention, including Arabian Heavy, Arabian Light, other Gulf crudes, Brent, North Sea crudes, North and West African crudes, Indonesian, Chinese crudes and mixtures thereof, but also shale oil, tar sands, gas condensates and bio-based oils.
  • the crude oil used as feed to the process of the present invention preferably is conventional petroleum having an API gravity of more than 20° API as measured by the ASTM D287 standard. More preferably, the crude oil used in the process of the present invention is a light crude oil having an API gravity of more than 30° API. Most preferably, the crude oil used in the process of the present invention comprises Arabian Light Crude Oil. Arabian Light Crude Oil typically has an API gravity of between 32-36° API and a sulfur content of between 1.5-4.5 wt-%.
  • Petrochemicals or "petrochemical products” as used herein relates to chemical products derived from crude oil that are not used as fuels.
  • Petrochemical products include olefins and aromatics that are used as a basic feedstock for producing chemicals and polymers.
  • High-value petrochemicals include olefins and aromatics.
  • Typical high-value olefins include, but are not limited to, ethylene, propylene, butadiene, butylene-1, isobutylene, isoprene, cyclopentadiene and styrene.
  • Typical high-value aromatics include, but are not limited to, benzene, toluene, xylene and ethyl benzene.
  • fuels as used herein relates to crude oil-derived products used as energy carrier. Unlike petrochemicals, which are a collection of well-defined compounds, fuels typically are complex mixtures of different hydrocarbon compounds. Fuels commonly produced by oil refineries include, but are not limited to, gasoline, jet fuel, diesel fuel, heavy fuel oil and petroleum coke.
  • gases produced by the crude distillation unit or “gases fraction” as used herein refers to the fraction obtained in a crude oil distillation process that is gaseous at ambient temperatures.
  • the "gases fraction” derived by crude distillation mainly comprises C1-C4 hydrocarbons and may further comprise impurities such as hydrogen sulfide and carbon dioxide.
  • other petroleum fractions obtained by crude oil distillation are referred to as “naphtha”, “kerosene”, “gasoil” and “resid”.
  • naphtha, kerosene, gasoil and resid are used herein having their generally accepted meaning in the field of petroleum refinery processes; see Alfke et al.
  • naphtha relates to the petroleum fraction obtained by crude oil distillation having a boiling point range of about 20-200 °C, more preferably of about 30-190 °C.
  • light naphtha is the fraction having a boiling point range of about 20-100 °C, more preferably of about 30-90 °C.
  • Heavy naphtha preferably has a boiling point range of about 80-200 °C, more preferably of about 90-190 °C.
  • the term "kerosene” as used herein relates to the petroleum fraction obtained by crude oil distillation having a boiling point range of about 180-270 °C, more preferably of about 190-260 °C.
  • the term "gasoil” as used herein relates to the petroleum fraction obtained by crude oil distillation having a boiling point range of about 250-360 °C, more preferably of about 260-350 °C.
  • the term “resid” as used herein relates to the petroleum fraction obtained by crude oil distillation having a boiling point of more than about 340 °C, more preferably of more than about 350 °C.
  • refinery unit relates to a section of a petrochemical plant complex for the chemical conversion of crude oil to petrochemicals and fuels.
  • a unit for olefins synthesis such as a steam cracker, is also considered to represent a "refinery unit”.
  • different hydrocarbons streams produced by refinery units or produced in refinery unit operations are referred to as: refinery unit-derived gases, refinery unit-derived light-distillate, refinery unit-derived middle-distillate and refinery unit-derived heavy-distillate. Accordingly, a refinery unit derived distillate is obtained as the result of a chemical conversion followed by a separation, e.g.
  • refinery unit-derived gases relates to the fraction of the products produced in a refinery unit that is gaseous at ambient temperatures. Accordingly, the refinery unit-derived gas stream may comprise gaseous compounds such as LPG and methane. Other components comprised in the refinery unit-derived gas stream may be hydrogen and hydrogen sulfide.
  • light-distillate, middle-distillate and heavy-distillate are used herein having their generally accepted meaning in the field of petroleum refinery processes; see Speight, J. G. (2005) loc.cit.
  • the refinery-unit derived light-distillate is the hydrocarbon distillate obtained in a refinery unit process having a boiling point range of about 20-200 °C, more preferably of about 30-190 °C.
  • the "light-distillate" is often relatively rich in aromatic hydrocarbons having one aromatic ring.
  • the refinery-unit derived middle-distillate is the hydrocarbon distillate obtained in a refinery unit process having a boiling point range of about 180-360 °C, more preferably of about 190-350 °C.
  • the "middle-distillate” is relatively rich in aromatic hydrocarbons having two aromatic rings.
  • the refinery-unit derived heavy-distillate is the hydrocarbon distillate obtained in a refinery unit process having a boiling point of more than about 340 °C, more preferably of more than about 350 °C.
  • the "heavy-distillate" is relatively rich in hydrocarbons having condensed aromatic rings.
  • alkane or "alkanes” is used herein having its established meaning and accordingly describes acyclic branched or unbranched hydrocarbons having the general formula C n H 2n+2 , and therefore consisting entirely of hydrogen atoms and saturated carbon atoms; see e.g. IUPAC. Compendium of Chemical Terminology, 2nd ed. (1997 ).
  • alkanes accordingly describes unbranched alkanes ("normal-paraffins” or "n-paraffins” or “n-alkanes”) and branched alkanes ("isoparaffins” or “iso-alkanes”) but excludes naphthenes (cycloalkanes).
  • aromatic hydrocarbons or "aromatics” is very well known in the art. Accordingly, the term “aromatic hydrocarbon” relates to cyclically conjugated hydrocarbon with a stability (due to delocalization) that is significantly greater than that of a hypothetical localized structure (e.g. Kekulé structure). The most common method for determining aromaticity of a given hydrocarbon is the observation of diatropicity in the 1H NMR spectrum, for example the presence of chemical shifts in the range of from 7.2 to 7.3 ppm for benzene ring protons.
  • naphthenic hydrocarbons or “naphthenes” or “cycloalkanes” is used herein having its established meaning and accordingly describes saturated cyclic hydrocarbons.
  • olefin is used herein having its well-established meaning. Accordingly, olefin relates to an unsaturated hydrocarbon compound containing at least one carbon-carbon double bond. Preferably, the term “olefins” relates to a mixture comprising two or more of ethylene, propylene, butadiene, butylene-1, isobutylene, isoprene and cyclopentadiene.
  • LPG refers to the well-established acronym for the term "liquefied petroleum gas”. LPG generally consists of a blend of C2-C4 hydrocarbons i.e. a mixture of C2, C3, and C4 hydrocarbons.
  • BTX One of the petrochemical products produced in the process of the present invention is BTX.
  • the term "BTX" as used herein relates to a mixture of benzene, toluene and xylenes.
  • the product produced in the process of the present invention comprises further useful aromatic hydrocarbons such as ethylbenzene.
  • the present invention preferably provides a process for producing a mixture of benzene, toluene xylenes and ethylbenzene (“BTXE").
  • the product as produced may be a physical mixture of the different aromatic hydrocarbons or may be directly subjected to further separation, e.g. by distillation, to provide different purified product streams.
  • Such purified product stream may include a benzene product stream, a toluene product stream, a xylene product stream and/or an ethylbenzene product stream.
  • C# hydrocarbons wherein "#” is a positive integer, is meant to describe all hydrocarbons having # carbon atoms.
  • C#+ hydrocarbons is meant to describe all hydrocarbon molecules having # or more carbon atoms.
  • C5+ hydrocarbons is meant to describe a mixture of hydrocarbons having 5 or more carbon atoms.
  • C5+ alkanes accordingly relates to alkanes having 5 or more carbon atoms.
  • the process of the present invention involves crude distillation, which comprises separating different crude oil fractions based on a difference in boiling point.
  • the term "crude distillation unit” or “crude oil distillation unit” relates to the fractionating column that is used to separate crude oil into fractions by fractional distillation; see Alfke et al. (2007) loc.cit.
  • the crude oil is processed in an atmospheric distillation unit to separate gas oil and lighter fractions from higher boiling components (atmospheric residuum or "resid").
  • it is not required to pass the resid to a vacuum distillation unit for further fractionation of the resid, and it is possible to process the resid as a single fraction.
  • vacuum distillation unit In case of relatively heavy crude oil feeds, however, it may be advantageous to further fractionate the resid using a vacuum distillation unit to further separate the resid into a vacuum gas oil fraction and vacuum residue fraction.
  • the vacuum gas oil fraction and vacuum residue fraction may be processed separately in the subsequent refinery units.
  • the vacuum residue fraction may be specifically subjected to solvent deasphalting before further processing.
  • the term "vacuum gas oil” as used herein relates to the petroleum fraction obtained by crude oil distillation having a having a boiling point range of about 340-560 °C, more preferably of about 350-550 °C.
  • the term "vacuum resid" as used herein relates to the petroleum fraction obtained by crude oil distillation having a boiling point of more than about 540 °C, more preferably of more than about 550 °C.
  • hydrocracker unit or “hydrocracker” relates to a refinery unit in which a hydrocracking process is performed i.e. a catalytic cracking process assisted by the presence of an elevated partial pressure of hydrogen; see e.g. Alfke et al. (2007) loc.cit.
  • the products of this process are saturated hydrocarbons, naphthenic (cycloalkane) hydrocarbons and, depending on the reaction conditions such as temperature, pressure and space velocity and catalyst activity, aromatic hydrocarbons including BTX.
  • the process conditions used for hydrocracking generally includes a process temperature of 200-600 °C, elevated pressures of 0.2-20 MPa, space velocities between 0.1-10 h -1 .
  • Hydrocracking reactions proceed through a bifunctional mechanism which requires an acid function, which provides for the cracking and isomerization and which provides breaking and/or rearrangement of the carbon-carbon bonds comprised in the hydrocarbon compounds comprised in the feed, and a hydrogenation function.
  • Many catalysts used for the hydrocracking process are formed by combining various transition metals, or metal sulfides with the solid support such as alumina, silica, alumina-silica, magnesia and zeolites.
  • the hydrocracker feed used in the process of the present invention preferably comprises naphtha, kerosene and gasoil produced by crude oil distillation in the process and refinery unit-derived light-distillate and refinery unit-derived middle-distillate produced in the process.
  • the LPG produced in the process that is subjected to olefins synthesis preferably comprises LPG comprised in the gases fraction derived by crude distillation and LPG comprised in the refinery unit-derived gases.
  • the process of the present invention comprises subjecting refinery unit-derived light-distillate and naphtha to hydrocracking and subjecting refinery unit-derived middle-distillate and one or more selected from the group consisting of kerosene and gasoil to aromatic ring opening.
  • the carbon efficiency of the process of the present invention can be further improved.
  • the light-distillate produced by aromatic ring opening is combined with the naphtha and subjected to hydrocracking.
  • aromatic ring opening unit refers to a refinery unit wherein the aromatic ring opening process is performed.
  • Aromatic ring opening is a specific hydrocracking process that is particularly suitable for converting a feed that is relatively rich in aromatic hydrocarbon having a boiling point in the kerosene and gasoil boiling point range, and optionally the vacuum gasoil boiling point range, to produce LPG and, depending on the specific process and/or process conditions, a light-distillate (ARO-derived gasoline).
  • ARO process is for instance described in US3256176 and US4789457 .
  • Such processes may comprise of either a single fixed bed catalytic reactor or two such reactors in series together with one or more fractionation units to separate desired products from unconverted material and may also incorporate the ability to recycle unconverted material to one or both of the reactors.
  • Reactors may be operated at a temperature of 200-600 °C, preferably 300-400 °C, a pressure of 3-35 MPa, preferably 5 to 20MPa together with 5-20 wt-% of hydrogen (in relation to the hydrocarbon feedstock), wherein said hydrogen may flow co-current with the hydrocarbon feedstock or counter current to the direction of flow of the hydrocarbon feedstock, in the presence of a dual functional catalyst active for both hydrogenation-dehydrogenation and ring cleavage, wherein said aromatic ring saturation and ring cleavage may be performed.
  • Catalysts used in such processes comprise one or more elements selected from the group consisting of Pd, Rh, Ru, Ir, Os, Cu, Co, Ni, Pt, Fe, Zn, Ga, In, Mo, W and V in metallic or metal sulphide form supported on an acidic solid such as alumina, silica, alumina-silica and zeolites.
  • an acidic solid such as alumina, silica, alumina-silica and zeolites.
  • the term "supported on” as used herein includes any conventional way to provide a catalyst which combines one or more elements with a catalytic support.
  • the process can be steered towards full saturation and subsequent cleavage of all rings or towards keeping one aromatic ring unsaturated and subsequent cleavage of all but one ring.
  • the ARO process produces a light-distillate ("ARO-gasoline") which is relatively rich in hydrocarbon compounds having one aromatic and or naphthenic ring.
  • ARO-gasoline a light-distillate
  • a further aromatic ring opening process is described in US 7,513,988 .
  • the ARO process may comprise aromatic ring saturation at a temperature of 100-500 °C, preferably 200-500 °C, more preferably 300-500 °C, a pressure of 2-10 MPa together with 5-30 wt-%, preferably 10-30 wt-% of hydrogen (in relation to the hydrocarbon feedstock) in the presence of an aromatic hydrogenation catalyst and ring cleavage at a temperature of 200-600 °C, preferably 300-400 °C, a pressure of 1-12 MPa together with 5-20 wt-% of hydrogen (in relation to the hydrocarbon feedstock) in the presence of a ring cleavage catalyst, wherein said aromatic ring saturation and ring cleavage may be performed in one reactor or in two consecutive reactors.
  • the aromatic hydrogenation catalyst may be a conventional hydrogenation/hydrotreating catalyst such as a catalyst comprising a mixture of Ni, W and Mo on a refractory support, typically alumina.
  • the ring cleavage catalyst comprises a transition metal or metal sulphide component and a support.
  • the catalyst comprises one or more elements selected from the group consisting of Pd, Rh, Ru, Ir, Os, Cu, Co, Ni, Pt, Fe, Zn, Ga, In, Mo, W and V in metallic or metal sulphide form supported on an acidic solid such as alumina, silica, alumina-silica and zeolites.
  • the process can be steered towards full saturation and subsequent cleavage of all rings or towards keeping one aromatic ring unsaturated and subsequent cleavage of all but one ring.
  • the ARO process produces a light-distillate ("ARO-gasoline") which is relatively rich in hydrocarbon compounds having one aromatic ring.
  • ARO-gasoline a light-distillate
  • the process of the present invention comprises:
  • the carbon efficiency of the process of the present invention can be further improved.
  • the term "resid upgrading unit” relates to a refinery unit suitable for the process of resid upgrading, which is a process for breaking the hydrocarbons comprised in the resid and/or refinery unit-derived heavy-distillate into lower boiling point hydrocarbons; see Alfke et al. (2007) loc.cit.
  • Commercially available technologies include a delayed coker, a fluid coker, a resid FCC, a Flexicoker, a visbreaker or a catalytic hydrovisbreaker.
  • the resid upgrading unit may be a coking unit or a resid hydrocracker.
  • a “coking unit” is an oil refinery processing unit that converts resid into LPG, light-distillate, middle-distillate, heavy-distillate and petroleum coke. The process thermally cracks the long chain hydrocarbon molecules in the residual oil feed into shorter chain molecules.
  • the feed to resid upgrading preferably comprises resid and heavy-distillate produced in the process.
  • Such heavy-distillate may comprise the heavy-distillate produced by a steam cracker, such as carbon black oil and/or cracked distillate but may also comprise the heavy distillate produced by resid upgrading, which may be recycled to extinction. Yet, a relatively small pitch stream may be purged from the process.
  • the resid upgrading used in the process of the present invention is resid hydrocracking.
  • the carbon efficiency of the process of the present invention can be further improved.
  • a “resid hydrocracker” is an oil refinery processing unit that is suitable for the process of resid hydrocracking, which is a process to convert resid into LPG, light distillate, middle-distillate and heavy-distillate.
  • Resid hydrocracking processes are well known in the art; see e.g. Alfke et al. (2007) loc.cit. Accordingly, 3 basic reactor types are employed in commercial hydrocracking which are a fixed bed (trickle bed) reactor type, an ebullated bed reactor type and slurry (entrained flow) reactor type.
  • Fixed bed resid hydrocracking processes are well-established and are capable of processing contaminated streams such as atmospheric residues and vacuum residues to produce light- and middle-distillate which can be further processed to produce olefins and aromatics.
  • the catalysts used in fixed bed resid hydrocracking processes commonly comprise one or more elements selected from the group consisting of Co, Mo and Ni on a refractory support, typically alumina. In case of highly contaminated feeds, the catalyst in fixed bed resid hydrocracking processes may also be replenished to a certain extend (moving bed).
  • the process conditions commonly comprise a temperature of 350-450 °C and a pressure of 2-20 MPa gauge.
  • Ebullated bed resid hydrocracking processes are also well-established and are inter alia characterized in that the catalyst is continuously replaced allowing the processing of highly contaminated feeds.
  • the catalysts used in ebullated bed resid hydrocracking processes commonly comprise one or more elements selected from the group consisting of Co, Mo and Ni on a refractory support, typically alumina.
  • the small particle size of the catalysts employed effectively increases their activity (c.f. similar formulations in forms suitable for fixed bed applications). These two factors allow ebullated bed hydrocracking processes to achieve significantly higher yields of light products and higher levels of hydrogen addition when compared to fixed bed hydrocracking units.
  • the process conditions commonly comprise a temperature of 350-450 °C and a pressure of 5-25 MPa gauge.
  • Slurry resid hydrocracking processes represent a combination of thermal cracking and catalytic hydrogenation to achieve high yields of distillable products from highly contaminated resid feeds.
  • thermal cracking and hydrocracking reactions occur simultaneously in the fluidized bed at process conditions that include a temperature of 400-500 °C and a pressure of 15-25 MPa gauge.
  • Resid, hydrogen and catalyst are introduced at the bottom of the reactor and a fluidized bed is formed, the height of which depends on flow rate and desired conversion.
  • catalyst is continuously replaced to achieve consistent conversion levels through an operating cycle.
  • the catalyst may be an unsupported metal sulfide that is generated in situ within the reactor.
  • resid upgrading liquid effluent relates to the product produced by resid upgrading excluding the gaseous products, such as methane and LPG and the heavy distillate produced by resid upgrading.
  • the heavy-distillate produced by resid upgrading is preferably recycled to the resid upgrading unit until extinction.
  • a resid hydrocracker is preferred over a coking unit as the latter produces considerable amounts of petroleum coke that cannot be upgraded to high value petrochemical products.
  • it may be preferred to select a coking unit over a resid hydrocracker as the latter consumes considerable amounts of hydrogen. Also in view of the capital expenditure and/or the operating costs it may be advantageous to select a coking unit over a resid hydrocracker.
  • the resid is further fractionated using a vacuum distillation unit to separate the resid into a vacuum gas oil fraction and vacuum residue fraction
  • the vacuum gasoil thus obtained is preferably fed to the aromatic ring opening unit together with one or more other hydrocarbon streams that are relatively rich in aromatic hydrocarbons and which have a boiling point in the kerosene and gasoil boiling point range.
  • Such hydrocarbon streams that are relatively rich in aromatic hydrocarbons and which have a boiling point in the kerosene and gasoil boiling point range may be selected from the group consisting of kerosene, gasoil and middle-distillate.
  • the vacuum residue hydrocracking preferably is slurry resid hydrocracking as defined herein above.
  • preferably less than 50 wt-%, more preferably less than 40 wt-%, even more preferably less than 30 wt-%, particularly preferably less than 20 wt-%, more particularly preferably less than 10 wt-% and most preferably less 5 wt-% of the crude oil is converted into fuels in the process of the present invention.
  • unit for olefins synthesis relates to a unit wherein a process for the conversion of alkanes to olefins is performed.
  • This term includes any process for the conversion of hydrocarbons to olefins including, but not limited to non-catalytic processes such as pyrolysis or steam cracking, catalytic processes such as propane dehydrogenation or butane dehydrogenation, and combinations of the two such as catalytic steam cracking.
  • steam cracking relates to a petrochemical process in which saturated hydrocarbons are broken down into smaller, often unsaturated, hydrocarbons such as ethylene and propylene.
  • gaseous hydrocarbon feeds like ethane, propane and butanes, or mixtures thereof
  • liquid hydrocarbon feeds like naphtha or gasoil (liquid cracking)
  • the reaction temperature is 750-900 °C and the reaction is only allowed to take place very briefly, usually with residence times of 50-1000 milliseconds.
  • a relatively low process pressure is to be selected of atmospheric up to 175 kPa gauge.
  • the hydrocarbon compounds ethane, propane and butanes are separately cracked in accordingly specialized furnaces to ensure cracking at optimal conditions. After the cracking temperature has been reached, the gas is quickly quenched to stop the reaction in a transfer line heat exchanger or inside a quenching header using quench oil. Steam cracking results in the slow deposition of coke, a form of carbon, on the reactor walls. Decoking requires the furnace to be isolated from the process and then a flow of steam or a steam/air mixture is passed through the furnace coils. This converts the hard solid carbon layer to carbon monoxide and carbon dioxide. Once this reaction is complete, the furnace is returned to service.
  • the products produced by steam cracking depend on the composition of the feed, the hydrocarbon to steam ratio and on the cracking temperature and furnace residence time.
  • Light hydrocarbon feeds such as ethane, propane, butane or light naphtha give product streams rich in the lighter polymer grade olefins, including ethylene, propylene, and butadiene.
  • Heavier hydrocarbon full range and heavy naphtha and gas oil fractions also give products rich in aromatic hydrocarbons.
  • fractionation units are well known in the art and may comprise a so-called gasoline fractionator where the heavy-distillate ("carbon black oil”) and the middle-distillate (“cracked distillate”) are separated from the light-distillate and the gases.
  • a so-called gasoline fractionator where the heavy-distillate ("carbon black oil”) and the middle-distillate (“cracked distillate”) are separated from the light-distillate and the gases.
  • most of the light-distillate produced by steam cracking (“pyrolysis gasoline” or "pygas”
  • the gases may be subjected to multiple compression stages wherein the remainder of the light distillate may be separated from the gases between the compression stages.
  • acid gases may be removed between compression stages.
  • the gases produced by pyrolysis may be partially condensed over stages of a cascade refrigeration system to about where only the hydrogen remains in the gaseous phase.
  • the different hydrocarbon compounds may subsequently be separated by simple distillation, wherein the ethylene, propylene and C4 olefins are the most important high-value chemicals produced by steam cracking.
  • the methane produced by steam cracking is generally used as fuel gas, the hydrogen may be separated and recycled to processes that consume hydrogen, such as hydrocracking processes.
  • the acetylene produced by steam cracking preferably is selectively hydrogenated to ethylene.
  • the alkanes comprised in the cracked gas may be recycled to the process for olefins synthesis.
  • the olefin synthesis employed in the process of the present invention is selected from the group consisting of gas cracking (pyrolysis of C2-C4 hydrocarbons) and dehydrogenation of C3-C4 hydrocarbons. Accordingly, the process of the present invention preferably does not comprise liquid cracking (pyrolysis of C5+ hydrocarbons).
  • the carbon efficiency of an integrated process to convert crude oil into petrochemical products can be improved by converting one or more of naphtha, kerosene and gasoil to LPG and to subsequently subject said LPG to olefins synthesis, when compared to a process wherein the same crude oil fractions are directly subjected to liquid cracking.
  • the olefins synthesis comprises dehydrogenation of propane.
  • propane By converting one or more of naphtha, kerosene and gasoil produced by crude oil distillation in the process; and refinery unit-derived light-distillate and/or refinery unit-derived middle-distillate produced in the process to LPG, the propane comprised in the LPG is subjected to propane dehydrogenation to produce propylene and hydrogen, which is a much more carbon efficient method for producing olefins when compared to pyrolysis since in a propane dehydrogenation process, substantially no methane is produced.
  • olefins synthesis comprising propane dehydrogenation
  • the overall hydrogen balance of the integrated process can be improved.
  • a further advantage of integrating dehydrogenation process into integrated process is that a high-purity hydrogen stream is produced, which can be used as feed to hydrocracker/aromatic ring opening without expensive purification.
  • propane dehydrogenation unit as used herein relates to a petrochemical process unit wherein a propane feedstream is converted into a product comprising propylene and hydrogen.
  • butane dehydrogenation unit relates to a process unit for converting a butane feedstream into C4 olefins.
  • processes for the dehydrogenation of lower alkanes such as propane and butanes are described as lower alkane dehydrogenation process.
  • Processes for the dehydrogenation of lower alkanes are well-known in the art and include oxidative dehydrogenation processes and non-oxidative dehydrogenation processes.
  • the process heat is provided by partial oxidation of the lower alkane(s) in the feed.
  • the process heat for the endothermic dehydrogenation reaction is provided by external heat sources such as hot flue gases obtained by burning of fuel gas or steam.
  • the process conditions generally comprise a temperature of 540-700 °C and an absolute pressure of 25-500 kPa.
  • the UOP Oleflex process allows for the dehydrogenation of propane to form propylene and of (iso)butane to form (iso)butylene (or mixtures thereof) in the presence of a catalyst containing platinum supported on alumina in a moving bed reactor; see e.g. US 4,827,072 .
  • the Uhde STAR process allows for the dehydrogenation of propane to form propylene or of butane to form butylene in the presence of a promoted platinum catalyst supported on a zinc-alumina spinel; see e.g. US 4,926,005 .
  • the STAR process has been recently improved by applying the principle of oxydehydrogenation.
  • the Lummus Catofin process employs a number of fixed bed reactors operating on a cyclical basis.
  • the catalyst is activated alumina impregnated with 18-20 wt-% chromium; see e.g. EP 0 192 059 A1 and GB 2 162 082 A .
  • the Catofin process has the advantage that it is robust and capable of handling impurities which would poison a platinum catalyst.
  • the products produced by a butane dehydrogenation process depend on the nature of the butane feed and the butane dehydrogenation process used. Also the Catofin process allows for the dehydrogenation of butane to form butylene; see e.g. US 7,622,623 .
  • the olefins synthesis further comprises dehydrogenation of butane.
  • One or more of the butane species such as isobutane or butane-1 comprised in the LPG is subjected to butane dehydrogenation to produce butylenes and hydrogen, which is a much more carbon efficient method for producing olefins when compared to pyrolysis since in a butane dehydrogenation process, substantially no methane is produced.
  • the process of the present invention comprises both dehydrogenation of propane and dehydrogenation of butane, and a mixture of propane and butane is used as a feed for a combined propane/butane dehydrogenation process.
  • the combination of hydrocracking to prepare LPG in combination with the dehydrogenation of propane and butane is particularly used in the process of the present invention since only by hydrocracking a significant part of the crude oil is converted into propane and butane, which then can be very efficiently can be converted into the high-value petrochemicals propylene and butylenes.
  • the gases fraction produced by the crude distillation unit and the refinery unit-derived gases are subjected to gas separation to separate the different components, for instance to separate methane from LPG.
  • gas separation unit relates to the refinery unit that separates different compounds comprised in the gases produced by the crude distillation unit and/or refinery unit-derived gases.
  • Compounds that are separated to separate streams in the gas separation unit comprise ethane, propane, and butanes, and may be hydrogen and fuel gas mainly comprising methane. Any conventional method suitable for the separation of said gases may be employed in the context of the present invention. Accordingly, the gases may be subjected to multiple compression stages wherein acid gases such as CO 2 and H 2 S may be removed between compression stages. In a following step, the gases produced may be partially condensed over stages of a cascade refrigeration system to about where only the hydrogen remains in the gaseous phase. The different hydrocarbon compounds may subsequently be separated by distillation.
  • the process of the present invention further comprises subjecting naphtha to a first hydrocracking process to produce LPG and BTX and subjecting at least a portion of the refinery unit-derived light-distillate to a different second hydrocracking process to produce LPG and BTX.
  • the composition of naphtha commonly is very different from the composition of refinery unit-derived light-distillate, especially in terms of the aromatics content.
  • feed hydrocracker a first hydrocracker
  • second hydrocracker gasoline hydrocracker
  • the process conditions and catalyst can be specifically adapted to the feed, resulting in an improved yield and purity of the LPG and/or BTX produced by said hydrocrackers.
  • the process can be more easily adapted, e.g.
  • gasoline hydrocracking unit refers to a refinery unit for performing a hydrocracking process suitable for converting a complex hydrocarbon feed that is relatively rich in aromatic hydrocarbon compounds -such as refinery unit-derived light-distillate including, but not limited to, reformer gasoline, FCC gasoline and pyrolysis gasoline (pygas)- to LPG and BTX, wherein said process is optimized to keep one aromatic ring intact of the aromatics comprised in the GHC feedstream, but to remove most of the side-chains from said aromatic ring.
  • the main product produced by gasoline hydrocracking is BTX and the process can be optimized to provide chemicals-grade BTX.
  • the hydrocarbon feed that is subject to gasoline hydrocracking comprises refinery unit-derived light-distillate. More preferably, the hydrocarbon feed that is subjected to gasoline hydrocracking preferably does not comprise more than 1 wt-% of hydrocarbons having more than one aromatic ring.
  • the gasoline hydrocracking conditions include a temperature of 300-580 °C, more preferably of 450-580 °C and even more preferably of 470-550 °C. Lower temperatures must be avoided since hydrogenation of the aromatic ring becomes favourable.
  • the catalyst comprises a further element that reduces the hydrogenation activity of the catalyst, such as tin, lead or bismuth, lower temperatures may be selected for gasoline hydrocracking; see e.g.
  • WO 02/44306 A1 and WO 2007/055488 In case the reaction temperature is too high, the yield of LPG's (especially propane and butanes) declines and the yield of methane rises. As the catalyst activity may decline over the lifetime of the catalyst, it is advantageous to increase the reactor temperature gradually over the life time of the catalyst to maintain the hydrocracking conversion rate. This means that the optimum temperature at the start of an operating cycle preferably is at the lower end of the hydrocracking temperature range. The optimum reactor temperature will rise as the catalyst deactivates so that at the end of a cycle (shortly before the catalyst is replaced or regenerated) the temperature preferably is selected at the higher end of the hydrocracking temperature range.
  • the gasoline hydrocracking of a hydrocarbon feedstream is performed at a pressure of 0.3-5 MPa gauge, more preferably at a pressure of 0.6-3 MPa gauge, particularly preferably at a pressure of 1-2 MPa gauge and most preferably at a pressure of 1.2-1.6 MPa gauge.
  • a pressure of 0.3-5 MPa gauge more preferably at a pressure of 0.6-3 MPa gauge, particularly preferably at a pressure of 1-2 MPa gauge and most preferably at a pressure of 1.2-1.6 MPa gauge.
  • gasoline hydrocracking of a hydrocarbon feedstream is performed at a Weight Hourly Space Velocity (WHSV) of 0.1-10 h -1 , more preferably at a Weight Hourly Space Velocity of 0.2-6 h -1 and most preferably at a Weight Hourly Space Velocity of 0.4-2 h -1 .
  • WHSV Weight Hourly Space Velocity
  • the space velocity is too high, not all BTX co-boiling paraffin components are hydrocracked, so it will not be possible to achieve BTX specification by simple distillation of the reactor product.
  • the yield of methane rises at the expense of propane and butane.
  • preferred gasoline hydrocracking conditions thus include a temperature of 450-580 °C, a pressure of 0.3-5 MPa gauge and a Weight Hourly Space Velocity of 0.1-10 h -1 .
  • More preferred gasoline hydrocracking conditions include a temperature of 470-550 °C, a pressure of 0.6-3 MPa gauge and a Weight Hourly Space Velocity of 0.2-6 h -1 .
  • Particularly preferred gasoline hydrocracking conditions include a temperature of 470-550 °C, a pressure of 1-2 MPa gauge and a Weight Hourly Space Velocity of 0.4-2 h -1 .
  • feed hydrocracking unit refers to a refinery unit for performing a hydrocracking process suitable for converting a complex hydrocarbon feed that is relatively rich in naphthenic and paraffinic hydrocarbon compounds -such as straight run cuts including, but not limited to, naphtha- to LPG and alkanes.
  • the hydrocarbon feed that is subject to feed hydrocracking comprises naphtha and/or the light-distillate produced by aromatic ring opening.
  • the main product produced by feed hydrocracking is LPG that is to be converted into olefins (i.e. to be used as a feed for the conversion of alkanes to olefins).
  • the FHC process may be optimized to keep one aromatic ring intact of the aromatics comprised in the FHC feedstream, but to remove most of the side-chains from said aromatic ring.
  • the process conditions to be employed for FHC are comparable to the process conditions to be used in the GHC process as described herein above.
  • the FHC process conditions comprise a lower process temperature than the GHC process to reduce the methane make.
  • the FHC process conditions comprise a temperature of 300-450 °C, a pressure of 300-5000 kPa gauge and a Weight Hourly Space Velocity of 0.1-10 h -1 .
  • FHC conditions optimized to the ring-opening of aromatic hydrocarbons include a temperature of 300-400 °C, a pressure of 600-3000 kPa gauge and a Weight Hourly Space Velocity of 0.2-2 h -1 .
  • the FHC process can be optimized to open the aromatic ring of the aromatic hydrocarbons comprised in the FHC feedstream. This can be achieved by modifying the GHC process as described herein by increasing the hydrogenation activity of the catalyst, optionally in combination with selecting a lower process temperature, optionally in combination with a reduced space velocity.
  • preferred feed hydrocracking conditions thus include a temperature of 300-550 °C, a pressure of 300-5000 kPa gauge and a Weight Hourly Space Velocity of 0.1-10 h-1. More preferred feed hydrocracking conditions include a temperature of 300-450 °C, a pressure of 300-5000 kPa gauge and a Weight Hourly Space Velocity of 0.1-10 h -1 . Even more preferred FHC conditions optimized to the ring-opening of aromatic hydrocarbons include a temperature of 300-400 °C, a pressure of 600-3000 kPa gauge and a Weight Hourly Space Velocity of 0.2-2 h -1 .
  • the light-distillate produced by FHC which is relatively rich in aromatic hydrocarbons, is subsequently subjected to GHC to ensure that all co-boilers of BTX are converted so that on-spec benzene can be produced by simple distillation without the need of extraction.
  • the process of the present invention may require removal of sulfur from certain crude oil fractions to prevent catalyst deactivation in downstream refinery processes, such as catalytic reforming or fluid catalytic cracking.
  • a hydrodesulfurization process is performed in a "HDS unit” or “hydrotreater”; see Alfke (2007) loc. cit.
  • the hydrodesulfurization reaction takes place in a fixed-bed reactor at elevated temperatures of 200-425 °C, preferably of 300-400 °C and elevated pressures of 1-20 MPa gauge, preferably 1-13 MPa gauge in the presence of a catalyst comprising elements selected from the group consisting of Ni, Mo, Co, W and Pt, with or without promoters, supported on alumina, wherein the catalyst is in a sulfide form.
  • the process of the present invention may further comprise hydrodealkylation of BTX to produce benzene.
  • BTX (or only the toluene and xylenes fraction of said BTX produced) is contacted with hydrogen under conditions suitable to produce a hydrodealkylation product stream comprising benzene and fuel gas mainly consisting of methane.
  • the process step for producing benzene from BTX may include a step wherein the benzene comprised in the hydrocracking product stream is separated from the toluene and xylenes before hydrodealkylation.
  • the advantage of this separation step is that the capacity of the hydrodealkylation reactor is increased.
  • the benzene can be separated from the BTX stream by conventional distillation.
  • hydrodealkylation Processes for hydrodealkylation of hydrocarbon mixtures comprising C6-C9 aromatic hydrocarbons are well known in the art and include thermal hydrodealkylation and catalytic hydrodealkylation; see e.g. WO 2010/102712 A2 .
  • Catalytic hydrodealkylation is preferred in the context of the present invention as this hydrodealkylation process generally has a higher selectivity towards benzene than thermal hydrodealkylation.
  • the hydrodealkylation catalyst is selected from the group consisting of supported chromium oxide catalyst, supported molybdenum oxide catalyst, platinum on silica or alumina and platinum oxide on silica or alumina.
  • the process conditions useful for hydrodealkylation can be easily determined by the person skilled in the art.
  • the process conditions used for thermal hydrodealkylation are for instance described in DE 1668719 A1 and include a temperature of 600-800 °C, a pressure of 3-10 MPa gauge and a reaction time of 15-45 seconds.
  • the process conditions used for the preferred catalytic hydrodealkylation are described in WO 2010/102712 A2 and preferably include a temperature of 500-650 °C, a pressure of 3.5-8 MPa gauge, preferably of 3.5-7 MPa gauge and a Weight Hourly Space Velocity of 0.5-2 h -1 .
  • the hydrodealkylation product stream is typically separated into a liquid stream (containing benzene and other aromatics species) and a gas stream (containing hydrogen, H 2 S, methane and other low boiling point hydrocarbons) by a combination of cooling and distillation.
  • the liquid stream may be further separated, by distillation, into a benzene stream, a C7 to C9 aromatics stream and optionally a middle-distillate stream that is relatively rich in aromatics.
  • the C7 to C9 aromatic stream may be fed back to reactor section as a recycle to increase overall conversion and benzene yield.
  • the aromatic stream which contains polyaromatic species such as biphenyl, is preferably not recycled to the reactor but may be exported as a separate product stream and recycled to the integrated process as middle-distillate ("middle-distillate produced by hydrodealkylation").
  • the gas stream contains significant quantities of hydrogen may be recycled back the hydrodealkylation unit via a recycle gas compressor or to any other refinery unit comprised in the process of the present invention that uses hydrogen as a feed.
  • a recycle gas purge may be used to control the concentrations of methane and H 2 S in the reactor feed.
  • the present specification includes a process installation to convert crude oil into petrochemical products comprising
  • an inlet for X or "an outlet of X", wherein "X" is a given hydrocarbon fraction or the like relates to an inlet or outlet for a stream comprising said hydrocarbon fraction or the like.
  • said direct connection may comprise further units such as heat exchangers, separation and/or purification units to remove undesired compounds comprised in said stream and the like.
  • feedstreams may be combined to form one single inlet into the refinery unit or may form separate inlets to the refinery unit.
  • the crude distillation unit (10) further comprises an outlet for gases fraction (230).
  • the LPG produced by hydrocracking (210) and LPG comprised in the gases fraction obtained by crude oil distillation and refinery unit-derived LPG produced in the integrated process (220) may be combined to form the inlet for LPG produced by the integrated petrochemical process installation (200).
  • one or more of naphtha, kerosene and gasoil produced by the crude oil distillation unit (310) may be combined with refinery unit-derived light-distillate and/or refinery unit-derived middle-distillate produced in the integrated petrochemical process installation (320) to form the inlet for a hydrocracker feed (301).
  • the process installation comprises: an aromatic ring opening unit (22) comprising an inlet for one or more selected from the group consisting of kerosene and gasoil (330) and refinery unit-derived middle-distillate (331) and an outlet for LPG produced by aromatic ring opening (222) and an outlet for light-distillate produced by aromatic ring opening (322).
  • an aromatic ring opening unit (22) comprising an inlet for one or more selected from the group consisting of kerosene and gasoil (330) and refinery unit-derived middle-distillate (331) and an outlet for LPG produced by aromatic ring opening (222) and an outlet for light-distillate produced by aromatic ring opening (322).
  • the hydrocracker (20) preferably comprises an inlet for a hydrocracker feed comprising naphtha produced by the crude oil distillation unit (311), which preferably is combined with refinery unit-derived light-distillate produced the integrated petrochemical process installation (321).
  • the crude distillation unit (10) comprises one or more outlets for gases fraction (230), naphtha (311), one or more of kerosene and gasoil (330), and resid (400); see Fig. 4 .
  • the process installation further comprises a resid upgrading unit (40) comprising an inlet for resid (400) and refinery unit-derived heavy-distillate (401) and an outlet for LPG produced by resid upgrading (223), an outlet for light-distillate produced by resid upgrading (323)and an outlet for middle-distillate produced by resid upgrading (333).
  • the resid upgrading unit (40) may further comprise an outlet for heavy-distillate produced by resid upgrading (420) which may be recycled to the resid upgrading unit (40) to further upgrade said heavy-distillate.
  • the process installation comprises at least two distinct hydrocrackers, wherein the first hydrocracker (23) (“feed hydrocracker”) comprising an inlet for naphtha (311) and an outlet for LPG produced by feed hydrocracking (212) and an outlet for BTX (600); and the second hydrocracker (24) (“gasoline hydrocracker”) comprising an inlet for at least a portion of the refinery unit-derived light-distillate (325) and an outlet for LPG produced by gasoline hydrocracking (213) and an outlet for BTX (600).
  • feed hydrocracker comprising an inlet for naphtha (311) and an outlet for LPG produced by feed hydrocracking (212) and an outlet for BTX (600)
  • gasoline hydrocracker (“gasoline hydrocracker") comprising an inlet for at least a portion of the refinery unit-derived light-distillate (325) and an outlet for LPG produced by gasoline hydrocracking (213) and an outlet for BTX (600).
  • Feed hydrocracker (23) preferably comprises an inlet for a hydrocracker feed comprising naphtha produced by the crude oil distillation unit (311), which may be combined with refinery unit-derived light-distillate produced the integrated petrochemical process installation (321), preferably refinery unit-derived light-distillate having a relatively low aromatics content.
  • the process installation further comprises:
  • the gas separation unit (50) further comprises an outlet for methane (701).
  • the ethane cracker (31) may further comprise an outlet for hydrogen produced by ethane cracking (810) and an outlet for methane produced by ethane cracking (710).
  • the propane dehydrogenation unit (32) may further comprise an outlet for hydrogen produced by propane dehydrogenation (820).
  • the gas separation unit (50) further comprises an outlet for butane (260), wherein said process installation further comprises a butane dehydrogenation unit (33) comprising an inlet for butane (260) and an outlet for butylenes (530).
  • the butane dehydrogenation unit (33) may further comprise an outlet for hydrogen produced by butane dehydrogenation (830).
  • Non-desired products such as non-high-value petrochemicals may be recycled to the appropriate unit to convert such a non-desired product to either a desired product (e.g. a high-value petrochemical) or to a product that is a suitable as feed to a different unit.
  • a desired product e.g. a high-value petrochemical
  • a product that is a suitable as feed to a different unit This is presented in figure 4 (Fig. 4 ).
  • light-distillate produced by resid upgrading (323) which has a relatively low aromatics content, may be recycled to hydrocracking, preferably feed hydrocracking.
  • the middle-distillate produced by resid upgrading (333) may be recycled to hydrocracking, preferably to aromatic ring opening.
  • all methane produced is collected and preferably subjected to a separation process to provide fuel gas.
  • Said fuel gas is preferably used to provide the process heat in the form of hot flue gases produced by burning the fuel gas or by forming steam.
  • the methane can be subjected to steam reforming to produce hydrogen.
  • the undesired side products produce by e.g. steam cracking may be recycled.
  • the carbon black oil and cracked distillate produced by steam cracking may be recycled to aromatic ring opening.
  • the different units operated in the process or the process installation are furthermore integrated by feeding the hydrogen produced in certain processes, such as in olefins synthesis, as a feedstream to processes that need hydrogen as a feed, such as in hydrocracking.
  • processes that need hydrogen as a feed such as in hydrocracking.
  • reforming of additional methane or fuel gas than the fuel gas produced by the process or the process installation may be required.
  • the products that are derived from the crude oil are divided into petrochemicals (olefins and BTXE, which is an acronym for BTX + ethylbenzene) and other products (hydrogen, methane and heavy fractions comprising C9 resin feed, cracked distillate, carbon black oil and resid).
  • petrochemicals organic compound
  • BTXE ethylbenzene
  • hydrogen, methane and heavy fractions comprising C9 resin feed, cracked distillate, carbon black oil and resid.
  • the total amount sums up to 100% of the total crude, since the resid is also taken into account.
  • From the product slate of the crude oil the carbon efficiency is determined as: Total Carbon Weight in petrochemicals / Total Carbon Weight in Crude .
  • Example 1 is identical to the Comparative Example except for the following: First, the naphtha fraction of the distillation is converted in a FHC unit to yield BTX (product) and LPG (intermediate). This LPG is separated into ethane-, propane- and butane fractions which are steam cracked.
  • the kerosene and gas oil fractions are subjected to aromatic ring opening that is operated under process conditions to maintain 1 aromatic ring.
  • the effluent from the aromatic ring opening unit is further treated in a GHC unit to yield BTX (product) and LPG (intermediate).
  • BTX product
  • LPG intermediate
  • Table 1 as provided herein below displays the total product slate from the steam cracker (cracked lights, naphtha and LPG) and from the FHC and GHC unit (BTX product) in wt% of the total crude.
  • the table also contains the remaining atmospheric residue fraction.
  • Example 1 the carbon efficiency is 42.3 wt-%.
  • Example 2 is identical to Example 1 except for the following: First, the resid is upgraded in a resid hydrocracker to produce gases, light-distillate and middle-distillate.
  • the gases produced by resid hydrocracking are being steam cracked.
  • the light-distillate produced by resid hydrocracking is being fed to the FHC unit to yield BTX (product) and LPG (intermediate).
  • BTX product
  • LPG intermediate
  • This LPG is separated into ethane- , propane- and butane fractions which are steam cracked.
  • the middle-distillate produced by resid hydrocracking are subjected to aromatic ring opening that is operated under process conditions to maintain 1 aromatic ring.
  • the effluent from the aromatic ring opening is further treated in a GHC unit to yield BTX and LPG.
  • This LPG is separated into ethane-, propane- and butane fractions which are steam cracked.
  • the heavy part of the cracker effluent (C9 resin feed, cracked distillate and carbon black oil) is being recycled to the resid hydrocracker.
  • the ultimate conversion in the resid hydrocracker is close to completion (the pitch of the resid hydrocracker is 2 wt% of the crude).
  • Table 1 displays the total product slate of the crude oil from the steam cracker (cracked products of lights, naphtha and LPG) and from the FHC and GHC units (BTX product) in wt% of the total crude.
  • the product slate also contains the pitch of the hydrocracker (2 wt % of the crude).
  • Example 2 the carbon efficiency is 80.9 wt-%.
  • Example 3 is identical to Example 2 except for the following: The propane and butane from the ARO - GHC units are not being steam cracked but being dehydrogenated into propylene and butene (with ultimate selectivities of propane to propylene 90%, and n-butane to n-butene of 90% and i-butane to i-butene of 90%).
  • Table 1 as provided herein below displays the total product slate from the steam cracker (cracked products of lights, naphtha and LPG) and from the FHC and the GHC unit (BTX product) in wt% of the total crude.
  • the product slate also contains the pitch of the hydrocracker (2 wt % of the crude).

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Claims (4)

  1. Procédé intégré pour transformer du pétrole brut en produits pétrochimiques comprenant une distillation de pétrole brut, un hydrocraquage et une synthèse d'oléfines, ledit procédé comprenant la soumission d'une matière première d'hydrocraqueur à un hydrocraquage pour produire du GPL et du BTX et la soumission du GPL produit dans le procédé à une synthèse d'oléfines, ladite matière première d'hydrocraqueur comprenant :
    l'un ou plusieurs parmi du naphta, du kérosène et du gasoil produits par distillation de pétrole brut dans le procédé ; et
    un distillat léger dérivé d'unité de raffinerie et/ou un distillat intermédiaire dérivé d'unité de raffinerie produit dans le procédé, ledit procédé comprenant :
    (a) la soumission de pétrole brut à une distillation de pétrole brut pour produire une fraction de gaz, du naphta, du kérosène, du gasoil et une huile résiduelle ;
    (b) la soumission de l'huile résiduelle à une valorisation d'huile résiduelle pour produire du GPL, un distillat léger et un distillat intermédiaire ;
    (c) la soumission du distillat intermédiaire produit par valorisation d'huile résiduelle et l'un ou plusieurs choisis dans le groupe constitué de kérosène et de gasoil à une ouverture de cycle aromatique pour produire du GPL et un distillat léger ;
    (d) la soumission du distillat léger produit par valorisation d'huile résiduelle, de distillat léger produit par ouverture de cycle aromatique et de naphta à un hydrocraquage pour produire du GPL et du BTX ; et
    (e) la soumission du GPL produit dans le procédé intégré à une séparation de gaz pour séparer différent composés en des flux séparés, lesdits flux comprenant de l'éthane, du propane et du butane ; et
    (f) la soumission desdits flux à une synthèse d'oléfines, ladite synthèse d'oléfines comprenant la déshydrogénation de propane et la déshydrogénation de butane et un procédé combiné de déshydrogénation de propane/butane.
  2. Procédé selon la revendication 1, dans lequel la valorisation d'huile résiduelle est un hydrocraquage d'huile résiduelle.
  3. Procédé selon l'une quelconque des revendications 1 à 2, dans lequel au moins 50 % en poids du produit combiné de naphta, de kérosène et de gasoil par la distillation de pétrole brut dans le processus est soumis à un hydrocraquage.
  4. Procédé selon l'une quelconque des revendications 1 à 3, comprenant en outre la soumission de naphta à un premier procédé d'hydrocraquage pour produire du GPL et du BTX et la soumission d'au moins une partie du distillat léger dérivé d'unité de raffinerie à un deuxième procédé d'hydrocraquage pour produire du GPL et du BTX.
EP18205192.0A 2013-07-02 2014-06-30 Procédé pour la conversion de pétrole brut en produits pétrochimiques ayant une efficacité en carbone améliorée Active EP3460026B1 (fr)

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US20160369187A1 (en) 2016-12-22
EA201990641A1 (ru) 2019-08-30
ES2922104T3 (es) 2022-09-08
JP2019049006A (ja) 2019-03-28
EP3017019A1 (fr) 2016-05-11
EP3017019B1 (fr) 2018-12-19
EA033477B1 (ru) 2019-10-31
CN105473690B (zh) 2018-01-09
JP6683606B2 (ja) 2020-04-22
JP2016526596A (ja) 2016-09-05
KR20160029806A (ko) 2016-03-15
EA038963B1 (ru) 2021-11-16
CN105473690A (zh) 2016-04-06
EP3460026A1 (fr) 2019-03-27
JP6879990B2 (ja) 2021-06-02
US10676681B2 (en) 2020-06-09
WO2015000848A1 (fr) 2015-01-08

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